Coating compositions comprising alkyd resins prepared from styrene-maleic anhydride copolymers, polyol and fatty acid



United States Patent Ofi 3,357,930 Patented Dec. 12, 1967 ice 3,357,936 COATING COMPOSKTIONS COMPRESING ALKYD RESINS PREPARED FROM STYRENE-MALEIC ANHYDRIIDE COPOLYMERS, POLYOL AND FAT- TY ACID I Robert L. Zimmerman and Eugene R. Moore, Midland, and Dale M. Pickelman, Auburn, Mich, assiguors to The Dow Chemical Company, Midland, Mich, a corporation of Delaware N Drawing. Filed Feb. 5, 1964, Ser. No. 342,790 16 Claims. (Cl. 260-22) This invention relates to new polyester coating compositions and is more particularly concerned with novel coatings based on the reaction product of a polyol, a fatty acid, and a monovinylidene aromatic copolymer which contains anhydride groups and has a controlled composition and molecular weight.

It has now been found that by limiting the anhydride content of a vinylidene aromatic copolymer to a range of from more than 10 up to 20, most advantageously from 15 to 20 percent by weight, and limiting the number average molecular Weight to less than 10,000, preferably to between 1,000 and 5,000, and most advantageously to less than 1500, reaction products with polyols and fatty acids are obtained which can be successfully cooked by a conventional'alkyd process without premature gelation.

The compositions of this invention provide air drying or baking coatings of excellent clarity, flexibility, color, solvent resistance and mar resistance. The products of this invention have good dilutability with mineral spirits and many are fully soluble.

The vinylidene aromatic copolymer which is employed in this invention comprises at least 80 but less than 90 weight percent of a monovinylidene aromatic monomer such as styrene, vinyltoluene, a-methylstyrene, ar-chlorostyrene, or ar-diehlorostyrene and correspondingly, more than 10 up to 20 percent by weight of an cap-unsaturated cyclic anhydride, e.g. maleic anhydride, chlormaleic anhydride, dichlormaleic anhydride, citraconic anhydride, itaconic anhydride, phenyl maleic anhydride, or aconitic anhydride. Especially desirable are terpolymers of styrene or vinyltoluene and 15-45 Weight percent a-methylstyrene with maleic anhydride. The copolymer viscosity (10 Weight percent in MEK at 25 C.) is less than 1.7 cps. is preferably in the range of 0.6 to 0.9 cps. and is most advantageously less than 0.7 cps. The copolymer should be homogeneous in composition, that is, at least 90 percent must have an anhydride component composition within a range of 5 percent, and preferably within a range of 2 percent by fractionation analysis. It is preferred that the molecular weight distribution also be relatively uniform, or that the resin contain a minimum of very low molecular weight species (M 1000). The functionality, (combined anhydride content and molecular weight) where in fm =fractional weight of anhydride in copolymer, should be less than 20 preferably from 2 to 10 and most advantageously less than 6. The number average molecular weight (fi referred to in the application is that determined by vapor pressure osmometry.

Any of a Wide variety of polyols may be employed such as a lower alkylene glycol or polyglycol, glycerol, triethanolamine, pentaerthritol, trimethylolpropane, or similar polyols or mixtures thereof. Particularly advantageously are aromatic resins that function as polyols such as DER 332 epoxy resin (the diglycidyl ether of Bisphenol A), DER 661 epoxy resin (the reaction product of epichlorohydrin and Bisphenol A having an epoxide equivalent weight of 475-575), copolymers of styrene and allyl alcohol, Dow Resin 565 (the reaction product of one mole of Bisphenol A with 2 moles of propylene oxide), ethylene oxide adducts of Bisphenol A and the like, which surprisingly yield alkyds that are fully dilutable with mineral spirits. With liquid epoxy resins, coatings for metal that exhibit improved corrosion resistance are obtained.

The fatty acids which may be employed include the C -C fatty acids and especially the unsaturated fatty acids. The preferred acids have from 12 to 18 carbon atoms. Most advantageously the fatty acid is a C unsaturated acid.

:If desired, additional polyacids or anhydrides e.g. phthalic anhydride and maleic anhydride or mixtures thereof may be employed over and above the copolymeric resinous polyanhydride. 'Maleic anhydride is advantageously used in this way to produce water dilutable or reducible vehicles. 7

The polyol and fatty acid may be derived from an oil plus polyol by alcoholysis if desired. The oil length should be in the range of 27-75, preferably 50 to 60. This invention makes it possible to formulate to higher oil length than is generally practiced 'with the styrenated' alkyds of the prior art and still achieve desirable hardness and toughness of the vehicle.

A hydroxyl to carboxyl ratio of from 0.6 to 1.60 is possible although the more useful range is from 0.80 to 1.40. The generally preferred ratio is about 1.20.

An esterification catalyst such as p-toluene sulfonic acid may be employed, if desired. The cook can readily be reacted to an acid number of 100, and should be in the range of 50-100 for alkali soluble and water dilutable products. For solvent based coatings the final acid number will generally be less than 20 and preferably less than 10. Solvent cooking is preferred at temperatures ranging from about to 250 C. When the vinylidene copolymer has a viscosity 0.9 cps., a diglyceride procedure should be employed to minimize early gelation. The fatty acid and polyol or oil and polyol are first cooked to the calculated diglyceride composition for glycerol or the equivalent monoalcohol for any other polyol and then the vinylidene copolymer is added and co-reacted. Another useful procedure that can aid in avoiding premature gelation is to mix the vinylidene resin and the fatty acid and heat to 180 C. before adding the polyol. This high temperature tends to reverse the crosslinking reaction of polyol and resinous polyanhydride permitting the fatty acid to participate in the esterification in more favorable competition with the polyanhydride.

For most vinylidene copolymers of less than 0.9 cps. all ingredients can be charged at the start and reacted.

Maleinization (term used herein to denote any of the bah-unsaturated cyclic anhydrides as defined above) to produce Water dilutable systems can be carried out after a preliminary cook of vinylidene resin, polyol and fatty acid (Procedure A). Better film properties and more uniform solubility of the products are achieved, however, by first maleinizing the fatty acid followed by addition of vinylidene resin and polyol and reaction (Procedure B). Alternatcly, the fatty acid can be maleinized, the polyol added and cooked to a desired acid number and then the vinylidene resin added and reacted (Procedure C).

Although phth'alic anhydride or other polyanhydrides or polyacids beside maleic anhydride can be employed as indicated above, it should be emphasized that this is not required and is generally not preferred except for water dilutable vehicles because it tends to sacrifice oil length and produce softer coatings having less desirable properties.

. Reactive curing agents such as melamine or urea formaldehyde resins may be used With the alkyds of the present invention for baking enamel vehicles having excellent properties.

The invention is further illustrated by the following examples wherein all parts are by weight unless otherwise specified. The copolymers employed in the following examples were prepared by the method of copending application Ser. No. 33,376 filed June 2, 1960, Zimmerman et 211., now U.S. Patent 3,336,267.

The oil length=50 and the stoichiometry of total OH/ total COOH=1.20.

Example 3 Following the procedure of Example 2, 100 grams of a copolymer of styrene, 15.1 percent MA and 35 percent u-MS having a weight percent solution viscosity in MEK at C. of 0.677 cps. (M =1420; F=4.4) was heated with 131 grams TOFA and 28.6 grams glycerol for 18 hours at about 225 C. 9.9 cc. of water was re- Example 1 10 moved and the A.N.=13.0. The product was fully dilutable with mineral spirits. The oil length was 54, the ratio of An alkyd resin for use in a coating composition using t tal OH/ total COOH was 1.20. A 1 mil film, balked at a homoggneous Styrene /ma1eic anhydride copolymer and 175 C. for mmutespassed a conical bend test without a diglyceride of dehydrated Castor oil fatty acid 15 taihiregoragsed 1a) front impact of 20 1n.-lbs. and areverse imp c 1n.- s.

(DCO'FA) was prepar'ed m the followmg manner Following the above procedure the following compositions were prepared and tested, with the results as indicated.

Percent Vise. FA Gly. OH/CQOH O.L. Time 1390 A.N. F.I., ILL, Conical KHN MA (g.) (g.) Ratio in.-1bs. tn.-lbs. Bend 16.3 .740 I 142 31.0 1.2 66 12.5 10.9 16.3 P P P 30.8

19.1 .750 144 36.3 1.3 as 8.0 11.5 20.3 P... P10 P 27.0

19.1 .750 120 36.3 1.4 52 6.0 10.3 23.5 P P P 32.3

A mixture of: Example 4 A l bl l water diuta e akyd resin for use in a coating 4 gi il g qii fi g i fa gi gf 8 composition using a homogeneous styrene/maleic anhy- EP S u 1 v1 n a 200 dride copolymer, fatty acid, polyol and maleic anhydride Diglyceride of poo (DCOFA-l-Glycerol-cooked 40 f f was Prepared SC 150, a mixture of alkylbenzenes b. 200 C. G

(Azeotmpmg solvent) 89.1/ 10.9 8/ MA copolymer (10 percent sol. visc. in

was heated to 213-220 C. in a 2 liter kettle equipped MEK at 25 C.=0.86 cps.) 100 with stirrer, N bubbling tube, and sampling tube. Three TOFA (Acintol F A 3) 128 samples were taken before the gel point was reached. G1 m1 n 20 Each sample was diluted to 35-45 percent solids with a yce mixture of xylol/MIBK at 1/ l by volume. The solutions P'TSA were catalyzed so that the concentration of heavy metal Toluene 5 driers based on resin solids were 0.06 percent Pb 0.02 was heated to C for 5 hr d r V mm which 11.0 ml.

Percent and perpent Films Cast 10 mll H O was removed and the A.N reducer? to 16 cooled to tin plate panels were dried at room temperature and c and d 60 C. for three days. G

SaIEInple I eac- AN 3D 0 M '6; 1 mitemt Maielc anhydride 20 a r an e a 0 21 i Y 11 6 Bend lf Iodine crystal 0.3 and cooking continued for 2 /2 hrs. at 190220 C. The 2.7 32.9 0-8 Elm-. Passedu un A.N. was 57 (Alc. KOH determination) and 110 g. 3;? 35:? F; ggjigg gj 11:33:: 33 60 ethylene glycol butyl ether (45 percent based on resin solids), water and NH OI-I were added to give a 35 per- Er m l 2 cent solids solution having a pH in the range of 8-9. p e Devolatilized film properties were checked and clear An alkyd resin for use in a coating composition using tack-free films resulted.

a homogeneous styrene/maleic anhydride copolymer,

tall oil fatty acid (TOFA) and glycerol was prepared in Example 5 the following manner. imixture of: g. of a 89.1/ Following the procedure of Example 4 a mixture of 10.9 S/MA copolymer M =2050, F=4.6, having a 10 weight percent solution viscosity in MEK at 25 C. of G.

-1 li Pills Si 1 5 21 l gg FA i1)+ g 70 80.16/ 19.8 S/MA copolymer (10 percent soLvisc.

g YCEIO +0.2 g. p-T WaS 68.126 to MEK=142. M 23570. F=145 00 210-224 C. for 1.5 hours; 9.3 ml. H O were removed TOFA/PO 3 u 1 and the A.N.=21. The product was mineral spirits solua no ble. It was let down with xylol to 68.7 percent solids. The P' film was clear after one hour at C. under vacuum. 7 Toluene 5 continued for 2 /2 hours at 190-220 C. Ethylene glycol butyl ether, water and NH OH were added to give a 33.5

percent solids solution having a pH in the range of 9-10.

Devolatilized films were clear andtack-free. The TOFA/PO a-dduct was prepared by coreacting about equal moles of propylene oxide and tall oil fatty acid in the presence of dry Dowex 1-X8 ion exchange resin (chloride form, 200-400 mesh) overnight at 80 C. in a sealed tube.

Example 6 (Maleinization procedure B) A water-based alkyd resin for use in a coating composition using a homogeneous styrene/a-methylstyrene/maleic anhydride terpolymer (M =1960; F=6.6), fatty acid, polyol and maleic anhydride for maleinization of the PA was prepared in the following manner. A mixture of:

Soya fatty acids 94.4

Maleic anhydride 15.1 Iodine crystal 0.25

Toluene 6.6

was heated to 200 C. and held between ZOO-208 C. for 2 hrs.

100 grams of aterpolymer of styrene with 16.5 weight percent of maleic anhydride and 19.0 weight percent of (IL-methyl styrene having a viscosity at 25 C. of 0.876 cps. and 0.25 g. of p-TSA were added and heated to 233 C. when 34.9 of diethylene glycol was added and cooked for 1.3 hr. in a temperature range of 211-280" C. water, 7.8 ml., was removed. The-AN. was 48.5 and the oil length 46, R=0.686. Then ethylene glycol monobutyl ether (45 percent based on resin) and aqueuous ammonia were added diluting to -35 percent at pH 8-9. Tall oil fatty acid can be substituted for soya and propylene glycol or glycerine can be substituted for diethylene glycol. The physical properties of the clear films were checked on steel panels coated with iron phosphate at 50-120 mg. per sq. -ft. of surface area coated using a catalyst concentration of 0.475 weight percent of 6 percent cobalt cyclodex based on resin solids. Films were allowed to air dry and baked (1 hr. at 140? C.). They were cast from a 35 percent solids solution with a No. 42 wire wound Meyer rod. Tackiness was checking by placing a weight on tissue paper exposed to the film, then removing the weight and tissue rapidly. The remaining, if any, tissue indicated the degree of tackiness. Reverse impact was measured in in.- lbs. without crazing of the film. The xylol resistance was indicated by rubbing the film back and forth 20 times with a saturated tissue. After air drying for 30 days the films were tack-free and passed a reverse impact of 90 in.-1bs. Similar results were observed after air drying and then baking at 140 C.

Example 7 Following the procedure of Example 6, a coating composition was-prepared employing a polymer 'of styrene, u-methylstyrene (43' percent) and maleic anhydride (19.1 percent) which had a viscosity of 0.750 cps. 110.3 grams of tall oil fatty acid was employed instead of soya and 36.3 grams of glycerol. The oil length-Was 46; R=l.026; final A.N. was 68.6. Air dried films were tack-free and passed a reverse impact of 90 in.-lb

Example 8 (Maleinizarion procedure C) A water based alkyd resin for use in a coating composition using a homegeneous styrene/a-methylstyrene/maleic anhydride terpolymer, fatty acid, polyol and maleic anhydride for maleinization of the fatty acid was prepared in the following manner. A mixture of:

Tall oil fatty acid (Acintol FA 3) 95.6

Maleic anhydride 15.3

Iodine crystal 0.22

Benzene 4.3

was heated to ZOO-214 C. and held for 2 hrs. Then added 20.9 g. of ethylene glycol and the temperature held at 150l90 C. until 26 ml. H O was removed.

100 grams of the terpolymer employed in Example 6 and 0.22 grams of p-TSA were added and heating continued at 211-250 C. A total 7.6 ml. H O was removed in 0.5 hr. A.N 59.3 (Alc. KOH). The reaction mixture cooled down and ethylene glycol monobutyl ether (45 percent based on resin solids) and aqueous ammonia were added diluting to -35 percent solids at pH of 8-9. Air dried films (14 days) were tack free and passed a reverse impact of in.-lbs. 1

Example 9 An oil based alkyd resin-for use in a coating composition using a homogeneous styrene/ a-methylstyrene/maleic anhydride terpolymer, fatty acid and polyol was prepared in the following manner. A mixture of:

Glycerol 26.7

p-TSA 0.3

and cooking was continued from 210-250 C. for 2 hrs. removing 12.2 ml. H O. The A.N. was 15.1. The reaction mixture was cooled down and diluted with xylol to 50 percent solids. A clear viscous solution resulted Films were cast from a 35 percent solids solution with a No. 42 wound rod on a Bonderite 1000. Heavy metal naphthanates were used as the driers having a concentration based on resin solids of 0.06 percent Pb, 0.02 percent Mn, and 0.02 percent Co. Films dried for 5 days at room temperature, or 10 minutes at 175 C. passed a reverse impact of 90 in.-lbs. Resimene 882 (butylated melamine formaldehyde) and Cymel' 300 (hexamethylether of hexamethylol melamine) when co-cured with the above alkyd showed improved solvent and mar resistance and excellent flexibility.

Example 10 Oil based alkyd resins for use in a coating composition using a homogeneous styrene/a-methylstyrene/maleic anhydride terpolymer, fatty acid, and polyol were pre pared in the following manner:

( 1) Heat the polymeric anhydride (S/aMS/MA),

grams, fatty acid, azeotroping solvent to 200 C.

(2) Add the polyol or polymeric polyol and catalyst if indicated. t

(3) Cook until visc. build is sufiicient.

(4) Dilute with solvent to 50 percent solids.

(5 A.N. determined by an Alc. KOH titration in pyridine with thymol blue indicator.

Physical properties of the baked films /2 hr. at C. with drier concentration based on resin of 0.06 percent Pb, 0.02 percent Mn, 0.02 percent Co) Werechecked on Bonderite 1000 panels, cast from 35 percent solids with No. 42 wire wound rod. Theimpact, flexibility and hardness were checked with standard procedures. The xylol resistance was checked by a saturated tissue rub test. The

Knoop Hardness Number (KHN) was measured on a wherein fm fractional weight of anhydride in the co- Kentron Hardness Tester with 10X magnification. polymer, is less than 20.

Wt. Composition of MA Polymers Physical Proper., Drier Cone. Based on Res., .06 percent Pb, .02 percent Mn,

.02 percent (Cook hr. 175 C.)

M s 6'2 A A "6 Sam le 3 U L El 0: i:

p E E 2 e 5, m o E 2 0 F 5 o e a e g 5 2 a o 0 G1 .& 0 V Q Q m 2 H 2 5; 5 3 se a II a 5 E a i in a. 0. 2. #4 9-1 0 0 E- e g 4 m 0 4 M 1 30 5 0 701 TO 142.-- DER 332 1.20 48 Yes, p- 200-253 24 4.3 10.6 P 1? Good 11.4

epoxy TSA. resin 71.1. 2 39 10.5 0. 701 TO 242-.- DER 661 1.20 48 Yes, p- 200-255 5 0 6 13 6 P00 P do i7 9 epoxy TSA.

resin 104. 3 39 10.5 0. 701 TO 90.8-.- Gly 19.9--- 1.20 46 No 207-250 12 6.6 10.6 P11 F craze.- do- 19.5 4 39 7 10.7 0. 752 T0 92.5--- Gly 20.3--- 1.20 47 N0 200-210 8 7.0 16.5 P P ...do. 23.1 5 39 10.5 0.701 TO 242... 35 1003 1.00 39 YeTsSR- 200-240 17.6 9.05 P Fcraze do.. 28.9 6 39 10.5 0. 701 DCO 50.0- Glv1 3.25 1.065 41 No.-..'... 190-240 18 6.4 12. 1 P F craze. Fair... 7.3

PA 20.0 EG 11.5

l The copolymer employed in Sample 4 was fractionated to remove low molecular weight species, i.c., chains having a molecular weight of less than 1,000. The M -was 3,880; F=8.5.

2 Phthalic anhydride.

3 RI 100 is a copolymer of about 80 weight percent styrene and 20 weight percent allyl alcohol having a molecular weight of about 1,600.

4 Ethylene glycol.

In Sample 6 only 56.1 grams of the copolymer were 9. Composition of claim 8 wherein the functionality, employed.

Example 11 F f M The cooked product of Sample 1 from Example 10, 39.8 49 grams, Was dissolved at 50.4 percent solids in xylene.

Fifty grams of a mixture of 285 par/[S of F6203, 5 5 wherein jm=fractiona1 Weight of anhydride in the coparts of ASP-400 clay pigment and 43.0 parts of barium P iS from 2 to 10. lf t were added The mixture was ground in a Por 10. Composition of claim 6 wherein the polyol is a celain ball mill overnight, cut with 50 grams of SC 150, copolymer of Wrens anyl P and dn-ers added to 0.06 percent Pb m percent Mn and 11. Composition of claim 1 wherein the fatty acid has 0.02 percent Co (based on resin). One mil films were cast 40 from 8 to 22 f I on Bonderite 1000, baked at 175' C. for /2 hour and eX- composltlofl 1a1m 11 Wherem the fatty and 1S posed in a salt fog cabinet for 250 hrs. (Spray of salt fog an unsaturatedflcld havmgls carbon at 100 F. temperatures.) The films remained intact. oomposltlon of clalm 1 Whefeln the 011 length Failures up to at the scribe line were observed. from 25 to Various difi ti may be made in the present i 14. Composition of claim 1 which has been maleinized vention without departing from the spirit or scope thereof, to an acld l f of m to and it is understood that We limit ourselves only as defined Composltlofl 0f clalm 14 Whlch contams Water in the amended claims and ethylene glycol nionobutyl ether as a cosolvent.

We l 16. Article coated with a tightly adhering dried coating 1. Coating composition comprising the reaction product of the composltlon of clalm of (A) a vinylidene aromatic copolymer having more than 50 10 up to 20 weight percent of an a,B-unsaturated cyclic References Cited anhydride and a number average molecular Weight of less UNITED STATES PATENTS than 10,000, at least 90 percent of said copolymer hav- 2 537 949 1/1951 Adams 260 22 ing an anhydride component composition within a range 2:500:765 3/1950 M'onmgue of 5 percent by fractionation analysis, (B) a polyol and 2,561 313 7/1951 Malinowski 260*23 (C) a fatty acid in a proportion such that the hydroxyl 2320311 1/1958 Kiebler et a1 carbOXYI ratio is from 05 to 2,940,946 6/1960 Shokal et a1. 26023 2. Composition of claim 1 wherein the aromatic co- 3,056,108 11/1962 Broadhead polymer has a viscosity, 10 percent in methyl ethyl ketone 3,085,986 4/1963 Muskat 260*23 at e than P 3,098,834 7/1963 Jerabek 26023.7 3. Composition of claim 2 wherein the viscosity 18 from 3,139,411 6/1964 Bmckman at 260 22 (1610 3,194,774 7/1965 Nichols 26022 4. Composition of claim 1 wherein the copolymer is a 3 313 755 4/1967 ORourke copolymer of styrene and maleic anhydride. 3321424 5/1967 Imes et aL 260 23 5. Composition of claim 1 wherein the polymer is a terpolymer of a-methylstyrene, a second and different OTHER REFERENCES vinylidine aromatic compound and maleic anhydride. Payne: Organic Coating Technology, vol. I, 1954, pp.

6. Composition of claim 1 wherein the polyol is an aro- 2044, matic resinous polyol. Chatfield: Varnish Constituents, 1953, p. 270.

7. Composition of claim 6 wherein the polyol is an epoxy resin. DONALD E. CZAJA, Primary Examiner.

8. Composition of claim 1 wherein the functionality, LEON BERCOVITZ Examiner. F=fi$ R. WHITE, Assistant Examiner. 

1. COATING COMPOSITION COMPRISING THE REACTION PRODUCT OF (A) A VINYLIDENE AROMATIC COPOLYMER HAVING MORE THAN 10 UP TO 20 WEIGHT PERCENT OF AN A,B-UNSATURATED CYCLIC ANHYDRIDE AND A NUMBER AVERAGE MOLECULAR WEIGHT OF LESS THAN 10,000 AT LEAST 90 PERCENT OF SAID COPOLYMER HAVING AN ANHYDRIDE COMPONENT COMPOSITION WITHIN A RANGE OF 5 PERCENT BY FRACTIONATION ANALYSIS, (B) A POLYOL AND (C) A FATTY ACID IN A PROPORTION SUCH THAT THE HYDROXYL TO CARBOXYL RATIO IS FROM 0.6 TO 1.6. 